Method and composition for marking articles



Patented June 24, 1941 ARTICLES I Foster Dee Snell, New York, N. Y., assignor to Foster D. Snell, Inc.,

a corporation of New York No Drawing. Application March 28, 1939,

Serial No. 264,666

11 Claims. (01. rise- 11) This invention relates to the treatment of articles to make themfluorescent under the influence of light of short wave length. More particularly. the invention relates to the treatment of furs and skins at selected positions so as to provide an identification mark that is not re-- moved on scraping away the surface portion of the skin and that is invisible and, therefore, un-

objectionable in ordinary light but is readily visible in ultra-violet light. Theidentiflcation of f-ursgand skins is extremely important and heretofore has beendiflicult to accomplish. Marks commonly applied either are objectionably- -conspicuous or may be obliterated in the scraping away of fleshy materials during dressing of the raw skin.

Skins and furs, purchased in' lots that are frequntly very large, are usually sent by the buyer to one or more outside processors. Some of the processors dress the skins or furs. Others dye them. Because of the large value involved and the fact that the furs and skins differ very great- ;ly in quality, it has been not uncommon practice heretofore for certain unscrupulous processors to substitute articles of inferior quality for those supplied by a given buyer for processing.

To make such dishonest practice susceptible to detection without marring the fur or skin with objectionable marking is' an object of the invention. Another object is the provision of a mark that will survive long soaking in Water and removal of the surface portions of the skin during the dressing and dyeing. Other objects and advantages will appear from the detailed description that follows.

Briefly stated, the preferred embodiment of the invention includes the impregnation of furs,

skins, hides, leather penetrable to liquids, and,

similar articles, hereinafter referred to as articles including a member of skin, with a solution of a fluorescent substance in a solvent therefor. The invention includes also the herein described compositions for use in such impregnation.

In general, the preferred method of the invention includes impregnating a member of skin or the like withta solution of the fluorescent substance in a mobile liquid volatile solvent therefor that is substantially inert chemically'towards the said member and substance, removing the solvent, as by evaporation, and causing a substantial amount of the fluorescent substance to remain within the article.

The invention is illustrated more specifically by description in connection with the following examples.

The skin such as that of a fur article, say a raw rabbit skin, is treated at selected positions with my identifying composition. Thus, it is stamped with the monogram, signature, or other desired marking of the owner of the article. In case of a fur piece, the stamping is applied suitably to the side on which the skin is exposed.

' 'I'heidentifying composition used is a solution of a substance adapted to fiuoresce under the influence of light of short wave length, that is, of shorter wave length than that of the visible spectrum. Such fluorescent substances, for instance, are anthracene, quinine compounds, and menthyl or methyl anthranilate. 0f the above, the anthracene gives particularly favorable results and should be used for most purposes. Quinine compounds that have been used to advantage are the esters, such as. the oleate, stearate, and palmitate, introduced in solution in naphtha. For use on skins or the like, the substance should be insoluble in water after deposition within the skin. These identifying substances when impregnated into the skin are invisible in ordinary light.

As a solvent for the fluorescent substance there 'is usedone of the general properties stated above. Benzol, toluol, and xylol may be used, benzol being the most suitable ordinarily. Ether, alcohol or mixtures thereof may also be used, proper safety precautions to be observed when either ether or benzol is used. The solvent selected. (except in the case of ether) may be used in warmcondition, say at a temperature between F. and the boiling point of the solvent. Using the warm solvent is especially advantageous when it is desired to deposit the fluorescent substance within the article :by cooling a saturated solution of the said substance.

The solution of the fluorescent substance is suitably made concentrated, that is, nearly or quite saturated, when anthracene, for example, is used as the fluorescent substance, and the solution cooled after impregnation into the article to a temperature below the saturation point of the anthracene, so that the anthracene will crystallize or deposit within the skin or the like. i The solvent is then evaporated at a temperature below the said saturation point, so that a deposit of the fluorescent substance is left within the article.

' When precipitation within the skin is or is not efiected, the fluorescent substances are retained in large measure and fixed within the sln'n, as by absorption or other phenomenon which prevents the migration and complete removal of the said substances to the surface of the skin as the volatile solvent evaporates from the said surface.

This retention b particularly satisfactory when the treatment is applied to skins in the raw condition in which they are delivered to the worker by the trapper or grower.

As indicated, the solvent is removedpreferably by evaporation. It is necessary'that the evaporation be made at a temperature below that of deterioration of the skin or the article contain-,,

ing it.

Following the method illustrated, it is possible to leave within the skin such a deep and thorough impregnation with the fluorescent substance that subsequent removal of adhering fleshy material from the skin does not destroy the marking applied. Thus, the marked raw skin may be submitted to the dressing operation without obliteration of the mark, even though it is common in this dressing operation to soften the skin by soaking in water for a day or so and then to scrape from the inner side of the skin a substantial thickness of material.

More specifically, a solution that has been used with satisfaction in .the marking of skins or the like, as described, is one containing approximately 1.6 pounds of anthracene in gallons of benzol, 90% grade, the solution being maintained at about 100 F.

Possibly because of the solubility relations due to the presence in the skin of fats or oils that are soluble in and solvents for the volatile solvent as well as for anthracene or the like or possibly for other reasons, there is particularly good penetration and retention of the fluorescent substance within the skin.

In place of impregnation with a relatively mobile solution, there may be used a paste, particularly on the edge portions or other parts from which little material is to be removed subsequently and into which deep penetration is not necessary. For such paste there may be used a thick solution or suspension of the fluorescent substance in a non-volatile solvent or suspending agent therefor. There may be used, for example, one of the fluorescent substances described and one or more of the following materials: petrolatum, tricresyl phosphate, and dibutyl, diethyl or diamyl phthalate. A typical paste is one con.. taining 4 parts of anthracene in 96 parts of petrolatum.

In the treatment of articles that must remain very flexible or pliable there may be admixed a plasticizing agent for For such treatment there may be used, as plasticizer, one or more of the above-mentioned nonvolatile materials, such as petrolatum, phosphate, or a phthalic acid ester, as well as one of the volatile solvent described previously. The proportion of the plasticizer for most purposes should be less than that of the fluorescent substance, say 10 to 25 per cent of the weight thereof.

In addition to the fluorescent substance and solvent therefor, a penetrating agent may be used. The agent should be substantially inert chemically to the other ingredients of the composition and to the article being treated, soluble in the solvent used, and adapted 'to lower the tricresylwater and possessing the general properties stated, as, for instance, a sodium alkyl sulfate, Turkey red oil, or a naphthalene sulfonate.

Furthermore, the fluorescent substance may be produced in insoluble form within the article being treated, as by chemical reaction or precipitation from solution. Thus, quinine oleate, stearate, or the like, may be formed in situ, as by impregnating an article with a quinine sulphate solution and with a separate solution including a soap, both the solutions being aqueous. In some cases it i believed that the fluorescent substance reacts with the article being treated, to be fixed by primary or secondary types of chemical reaction, by actual formation of a new compound or by physical adsorption.

Or, an article containing the fluorescent substance dissolved in a suitable solvent may be soaked in a liquid that is miscible with the said solvent but either a precipitant for or a poor solvent forthe fluorescent substance. Thus, a skin impregnated with an alcohol solution of a fluorescent substance that is practically insoluble in water may be soaked in water until the alcohol 01' the olution is greatly diluted by water or substantially replaced thereby. The fluorescent substance is precipitated. In this manner,

quinine, for instance, may be deposited within a skin.

Another example of producing the fluorescent substance within the article to be treated is the following: An article is impregnated with a near- I ly saturated aqueous solution of quinine sulfate the fluorescent substance.

interfacial tension of the solvent against the may well be one of those commonly used with at about ordinary atmospheric temperature. The article is then soaked in a dilute aqueous solution containing sodium carbonate, ammonium hydroxide, or other weak base. After the treatment, the article isdried and any surface scum or efllorescence that is objectionable is removed by dipping the article in water.

When an inexpensive fluorescent material is demanded, fluorescent petrolatum may be used. Thus, petrolatum from Pennsylvania crude oil may be used either as a paste or in solution in one of the volatile solvents. Such a solution may be used to impregnate skins or the like.

In place of the articles described above, there may be used other penetrable articles to be treated with fluorescent material in the method described above. Thus, skins or the like may be substituted for some board, fabrics, or articles containing rials.

The fluorescent substances described are considered to be harmless to the processor as well as the wearer of a garment containing the materials.

It will be understood that the details given are for the purpose of illustration, not restriction, and that variations within the spirit of the invention are intended to be included within the scope of the appended cla I claim: 1 I

1. The method of treating an article including a member of skin which comprises impregnating the member with a solution containing a waterinsoluble substance that when impregnated is invisible in ordinary light but adapted to fluoresce under the influence of light of short wave length and a liquid that is a solvent for the said substance and substantially inert chemically towards the said substance and member and then evaporating the solvent from the solution at a temperature below that of deterioration of the skin,

IJHI'DOSGS by paper 01' cardthe said substance being adsorbed by the skin and being largely retained within the skin when the solvent is evaporated.

2. The method of treating an article including a skin which comprises impregnating the skin with a solution, including anthracene and a volatile mobile solvent adapted to penetrate the skin, and then removing the solvent at a temperature below that of deterioration of the skin, the anthracenebeing largely retained within the skin when the solvent is removed.

3. The treatment of an article including a member of skin which comprises impregnating the article with a fluorescent petrolatum.

V 4. A composition of matter for use in impregnating an article including a skin, which comprises a solution of a Water-insoluble fluorescent substance that when impregnated is invisible in ordinary light, a volatile solvent therefor, and a penetrating agent dissolved in the said solution, the penetrating agent having the property of lowering the interfacial tension of the solvent against the skin.

5. The method of treating an article which comprises impregnating into the article a concentrated warm solution of a fluorescent substance that when impregnated is invisible in ordinary light, cooling the solution within the article to a temperature below the saturation point of the solution, and then removing the solvent from the article at a temperature below the said saturation point.

6. The method of treating an article which comprises forming a solution of anthracene in a warm volatile solvent, impregnating the solution into the article, allowing the solution to cool to a temperature below that of saturation of the solvent so that particles of anthracene are formed within the said article, and then evaporating the solvent at a temperature below that at which the said solid particles dissolve completely in the solvent.

7. The method of treating an article which comprises impregnating into the article a solution of a fluorescent water-insoluble substance that when impregnated is invisible in ordinary light adapted to react with the composition of the article and be converted within the article to insoluble form.

8. The method of treating an article of low penetrability to liquid which comprises impregnating the article with a solution including a substance that when impregnated is invisible in ordinary light but adapted to fluoresce under the influence of light of short wave length, a solvent {or the fluorescent substance, and a penetrating agent that is soluble in the said solvent and adapted to lower the interfacial tension of the solution against the said article.

9. The method of treating an article of low penetrability to liquid which comprises impregnating the article with a solution including a substance that when impregnated is invisible in ordinary light but adapted to fluoresce under the influence of light of short wave length, a solvent for the fluorescent substance, and a penetrating agent that is soluble in the said solvent and adapted to lower the interfacial tension of the solvent against the said article.

10. The method of treating an article of low penetrability to liquid which comprises impregnating the article with a solution including a water-insoluble substance that when impregnated is adapted to fluoresce under the influence of light of short wave length, water, and a. watersoluble penetrating agent adapted to lower the interfacial tension of the water against the said article.

11. The method of treating an article which comprises impregnating into the article a solution of a fluorescent substance that when impregnated is invisible in ordinary light and is adapted to be converted by the article to insoluble form.

FOSTER DEE SNELL.

Patent No. 2,2l '7,2 59,.

cERtI-ImcAis or CORRECTION.

v June 2h; .9 m. FOSTER DEE SNELL.

It is hereby certified that error appears in the printed specification of the above numbered'patent requiring correction as follows: Page 1, seconci column, line 11.9, for the word "when" read "whether"; page 5, first column, line 114., claim 5; after "petro1atum"-and before the period insert i'n;e' solution in A volatile solvent and then evaporating the solvent,

"thepetroleum being adsorbed and being largely retained within the skin when the solvent is eveporated"; and second column, line 51 claim l0,be fore "adapted" insert invisible in ordinary light but--; and thst the said Letters Patentshould be reed with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 26th""de; of August, A. D. l9hl.

' Henry Van Arsdale, (Seal) Aoting Conimis sioner of Patents. 

